CN1434843A - Emulsion and water-repellent composition - Google Patents

Emulsion and water-repellent composition Download PDF

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Publication number
CN1434843A
CN1434843A CN01809791A CN01809791A CN1434843A CN 1434843 A CN1434843 A CN 1434843A CN 01809791 A CN01809791 A CN 01809791A CN 01809791 A CN01809791 A CN 01809791A CN 1434843 A CN1434843 A CN 1434843A
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composition
silicon
water
containing compound
combination
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CN1250657C (en
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岩户聪子
贺来群雄
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from JP2000155281A external-priority patent/JP2001335693A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/10—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing hydrolysable silane groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Paints Or Removers (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Silicon Polymers (AREA)

Abstract

A composition having water-repellency at high temperature is provided. Some of the invention compositions also exhibits oil-repellency at high temperature. The composition comprises a fluorocarbon silane or hydrolyzate thereof; a surfactant; a polymerizable, silicon-containing compound; and a catalyst.

Description

Emulsion and water-repellent composition
Technical field
The present invention relates to a kind of emulsion compositions of fluorocarbon silame or its hydrolysate and coating composition of producing with it of comprising.
Background technology
Once disclosed to provide certain that refuse the water characteristic to contain the silane water miscible liquid at substrate surface in the past.For example referring to United States Patent (USP) 4,648,904,4,757,106,4,990,377,5,196,054,5,550,184 and 5,664,014; European patent 0 748 357 and day number of patent application of the present disclosure flat 11 (1999)-181355.
For example, United States Patent (USP) 5,550,184 is open, by a kind of hydrolyzable organoalkoxysilane of emulsification in the presence of the middle and high HLB value of water emulsifying agent so that make this hydrolyzable organoalkoxysilane remain on basic hydrolyzable state fully, the reactive hydrolysis silane emulsion of being produced simultaneously.This emulsion can produce at substrate surface the long-lived coating of refusing the water characteristic is provided.
Day number of patent application of the present disclosure flat 11 (1999)-181355 discloses a kind of emulsion that comprises particular type silane hydrolyzate product, particular type silicon ester material and tensio-active agent.Yet this emulsion requires the pH value is adjusted to basic region, just can show and refuse water and heat-resistant quality.
Therefore, if can develop a kind of new emulsion or contain the coating of this emulsion, they do not require that this kind alkaline pH is regulated and just can show desired heat-resisting and water repellency that will be satisfying.
In addition, refuse the water characteristic though these emulsions show, they do not have the oil repellent energy.For example, the glass port of baker, cooking stove or baking box can be coated with by the layer that has that the emulsion of good water repellency forms under the high temperature, but its anti-oil stain ability is still very poor.Therefore, if can develop a kind of emulsion that had not only shown water repellency but also shown oil repellent, then also will be very satisfying for used for various applications.
Therefore, the coating of wishing to develop a kind of new emulsion or comprising this emulsion, it does not require the alkaline pH adjusting, does not perhaps need top disclosed metal hydroxides or chemical just can show desired heat-resisting and water repellency.
In addition, refuse the water characteristic though these emulsions show, they do not have the oil repellent energy.For example, the glass port of baker, cooking stove or baking box can be coated with by the layer that has that the emulsion of good water repellency forms under the high temperature, but its anti-oil stain ability is still very poor.Therefore, if can develop a kind of emulsion that had not only shown water repellency but also shown oil repellent, then also will be very satisfying for used for various applications.
Summary of the invention
A kind of composition comprises fluorocarbon silame or its hydrolysate, tensio-active agent, polymerizable silicon-containing compound and catalyzer.
Detailed Description Of The Invention
Fluorocarbon silame comprises at least a hydrolyzable fluorocarbon silame usually, and available R f-(CH 2) p-Si{-(O-CH 2CH 2) n-OR ' } 3Representative, wherein R fCan be one or more C 3-18Perfluoro alkyl group, each R ' can be C identical or different and independently 1-3Alkyl group or its combination, p=2～4, and n=2～10).Preferred R fIt is the mixing perfluoro alkyl group of 8～18 carbon atoms.
The example of fluorocarbon silame includes but not limited to, perfluor alkyl ethide three (2-(2-methoxy ethoxy) oxyethyl group) silane is if n is 2; And (2-(2-(2-methoxy ethoxy) oxyethyl group) oxyethyl group) silane, if n is 3; And their combination.This kind fluorocarbon silame or available commercial is arranged, perhaps can be by any means preparation well known by persons skilled in the art, as " Kir-Othmer Encyclopedia of Chemical Technology (chemical technology the complete works) " third edition, roll up 20 disclosed.For example, this fluorocarbon can be by US 5,550, and 184 disclosed method productions are received its disclosed content for referencial use at this.
Any tensio-active agent is as long as the hydrolysate of energy emulsification fluorocarbon silame all can use.This tensio-active agent normally HLB value is high enough to suppress fluorocarbon silane hydrolysis product (Self-condensation) tensio-active agent of condensation voluntarily.Term " HLB " is meant by ICIAmerica ' s, Inc. (Wilmington, Delaware); Adamson, A.W., " Surface Physical Chemistry " the 4th edition, John Wiley ﹠amp; Sons, New York, 1982) the HLB system that announces.This tensio-active agent can be negatively charged ion, positively charged ion, nonionic, both sexes or its combination.Preferred surfactants be the HLB value greater than 12, more preferably greater than 16 those.Generally speaking, the HLB value of tensio-active agent is low more, and the desired consumption of this tensio-active agent stable emulsion is just big more.Two or more kinds of miscible each other tensio-active agent is also capable of being combined usually or mix to use, as long as they are that HLB is high enough to suppress the fluorocarbon silane hydrolysis product tensio-active agent of condensation voluntarily.
The HLB value of nonionogenic tenside can be according to formula, and particularly the formula that proposes at the Griffin of the Atlas of U.S. company (present ICI America company) calculates.Yet, under the situation of anionic type or cation type, determine that by calculating the method for HLB value does not still have so far.But, the change of noticing emulsification property is to very responsive this fact of the change of HLB value, and Atlas company sets up and delivered a kind of basis and the emulsification of standard oil tested the method for determining the HLB value.Company beyond the Atlas has also set up and has been used to test the method for determining the HLB value.Yet, adopting all susceptible of proofs of any experimental technique, the HLB value of anionic type or cation type is all greater than 16.
The example of nonionogenic tenside includes but not limited to, R ' f-CH 2CH 2-O-(CH 2CH 2O) 11-H, C 9H 19-C 6H 4-O-(CH 2CH 2O) 50-H, other nonionogenic tensides and combination thereof.The example of cats product includes but not limited to R ' f-CH 2CH 2SCH 2CH (OH) CH 2N (CH 3) 3 +Cl -, other cats products and combination thereof.Examples of anionic surfactants includes but not limited to, C 12H 25(OCH 2CH 2) 4OSO 3 -NH 4 +, C 12H 27-C 6H 4-SO 3 -Na +, other anion surfactants and combination thereof.In each general formula, R ' fBe perfluoro alkyl group, have about 3～18 carbon atoms usually.Preferred surfactants is the nonionogenic tenside that has polyoxyethylene glycol in molecular chain.
The content of fluorocarbon silame in water-based emulsions can be about 0.1wt% or higher, preferred about 2～20wt%, and most preferably 7～15wt% is a benchmark with the emulsion gross weight.The weight ratio of fluorocarbon silame and tensio-active agent can be between about 1: 1～about 10: 1, and preferred about 10: 2～about 10: 5, more preferably 10: 3.
Any polymerizable, silicon-containing compound all can use, if it can with the fluorocarbon silane hydrolysis product copolymerization, thereby improve heat-resisting water characteristic, heat-resisting oily characteristic or the two of refusing of refusing.Suitable polymerizable silicon-containing compound comprises silicon ester, organosilane or its combination.
Suitable silicon ester can have general formula Si-R 4, wherein R is selected from OCH 3, OCH 2CH 3, (OCH 2CH 2) mOCH 3And one or more groups of combination, m=1～10 wherein, preferred 1～3.Because Si-((OCH 2CH 2) mOCH 3) 4The silicon ester water soluble of (m=1～3) representative, but so be dissolved in the water-base emulsion that contains the fluorocarbon silame hydrolysate Si-((OCH wherein its within a short period of time 2CH 2) 2OCH 3) 4The silicon ester of representative is preferred at present.
The mol ratio of silicon ester and fluorocarbon silame can be between about 0.3: 1～about 10: 1, and preferred 0.3: 1～5: 1, most preferably 0.4: 1～2: 1.Suitable organosilane comprises general formula R 2 qSi (OR 3) 4-qOrganoalkoxysilane, each R wherein 2Can be the alkyl group of 1～about 10 carbon atoms independently; Each R 3Can be identical or different and each be the alkyl group of 1～about 3 carbon atoms independently; Q=1～3.The example of suitable organosilane includes but not limited to, methoxy silane, Ethoxysilane, propoxy-silane and their combination.
The mol ratio of organoalkoxysilane and fluorocarbon silame can be between about 0.3: 1～about 10: 1, and preferred 0.3: 1～5: 1, most preferably 0.4: 1～2: 1.
Catalyzer can be acid or pH-conditioning agent.Aqueous acids such as phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, nitric acid, acetate, oxalic acid or its combination can be used as acid and are used for said composition.
At present preferred catalyzer if use silicon ester as silicon-containing compound, is phosphoric acid, boric acid or its combination.
If organosilane is used as silicon-containing compound, then top disclosed aqueous acid or alkaline aqueous solution such as ammonia, pyridine, sodium hydroxide or potassium hydroxide, useful as catalysts.Phosphate aqueous solution is especially suitable.
Catalyst consumption normally can produce effective quantity of the emulsion with disclosed characteristic.Its amount also can for: when adopting silicon ester, the pH value of emulsion can be adjusted to and be equal to or less than 4.5, preferably less than 2.2, for example about 2.0 consumption specifically depends on catalyzer.If use organosilane, then do not have restriction to pH.Yet, if the pH value of having relatively high expectations can use alkali aqueous solution that the pH value is adjusted to and be equal to or higher than 7.0, especially 7.0～12.
Refusing the water characteristic by the coating of this emulsion compositions production heat-resisting can be by being adjusted to basic region with its pH value, perhaps, if with silicon ester as silicon-containing compound, be acidified to acidic region, for example adopt phosphoric acid, boric acid or its combination, and be improved.
Emulsion compositions of the present invention can comprise pigment, sterilant, UV light absorber, antioxidant or other habitual additives, and its consumption is not to influence the heat-resisting water characteristic degree of being of refusing of stability of emulsion and coating.
Any method known to those skilled in the art all can be used for preparing emulsion compositions of the present invention.All compositions can lump together in any order, produce said composition.
Yet preferably, with surfactant dissolves in water, slowly add fluorocarbon silame then, so that make being suppressed of fluorocarbon silame from condensation, the hydrolyzed state of fluorocarbon silame is maintained, and stirs simultaneously, for example stirs, add desired any additives, catalyzer, add the polymerizable silicon-containing compound at last.Usually, the pH value is not subjected to remarkably influenced because of the adding of silicon-containing compound.This method can be used to best to suppress fluorocarbon silame from condensation and keep its hydrolyzed state.
Water-based emulsion of the present invention can be applied on any base material.By this emulsion is coated on the substrate surface subsequent drying, this base material can obtain to refuse water, refuses oil or not only refuse water but also refuse oily characteristic.The example of suitable base material includes but not limited to aluminium, stainless steel or other metal sheets, glass, sheet glass, ceramic tile, brick, concrete, stone, timber, masonry, fiber, leather, plastics or other base materials that can use under hot conditions.Water-based emulsion can adopt any method well known by persons skilled in the art to implement in the coating of substrate surface, for example, and dip-coating, spraying, spin-coating method, rolling method, or other well-known methods.Dip coating is preferred, because it does not damage the transparency of glass baseplate.
Also can implement heating to quicken drying process.Usually, drying is to carry out about 5 minutes～24 hours in about 100～350 ℃ temperature.
Have, before water-based emulsion of the present invention is coated on the base material, can apply a kind of silicon (silicone) compound, for example, silicon-dioxide is to form bottom or backing layer.By this emulsion is coated on this above layer, the heat-resisting water characteristic of refusing can keep for a long time.Be coated with the later base material of this emulsion compositions, need, can after its drying, wash with water to remove the residual surface promoting agent.
Embodiment
Provide the following examples to be intended to illustrate the present invention, should not limit the scope of the invention undeservedly.
The composition that uses in following application example and the Comparative Examples is as follows:
Fluorocarbon silame is by R f-(CH 2) 2-Si{-(O-CH 2CH 2) 2-OCH 3} 3The perfluoroalkyl silane of representative, wherein R fBe F (CH 2) kCH 2CH 2(k=6,1～2wt%; K=8,62～64wt%; K=10,23～30wt%; And k=12～18,2～6wt%).Tensio-active agent is by R F '-CH 2CH 2-O-(CH 2CH 2O) 11The nonionogenic tenside of-H representative, wherein R F 'Be the perfluoro alkyl group of 3～18 carbon atoms, obtain by E.I.Du Pont Company (Wilmington, Delaware).Silicon ester is four [2-(2-methoxy ethoxy) ethyl] silicon ester (Si (DEGM) 4).Adopt following general formula (CH 3) Si (OCH 3) 3Organoalkoxysilane (organic methoxy silane).These chemical are obtained by Kanto chemical company (Japan).
Application example 1
Nonionogenic tenside is dissolved in a kind of mixture of formation in the water according to the consumption of per 100 weight part fluorocarbon silames, 30 weight parts.Fluorocarbon silame slowly adds (2.1kg adds in the time at 30min) in this mixture according to the consumption that with the water-based emulsion gross weight is benchmark 10wt%, utilizes mechanical stirrer to stir therebetween.Being suppressed of fluorocarbon silame from condensation, and hydrolyzed state is kept.When ph value of emulsion is measured with pH meter, add phosphoric acid.When the pH value reaches 2.0, stop the adding of phosphoric acid.Add Si (DEGM) 4, make Si (DEGM) 4Mol ratio to fluorocarbon silame remains 0.45, and the result obtains a kind of water-based emulsion.
Then, water-based emulsion is coated on the aluminium sheet (JIS 1100,2.5cm * 5.0cm, thick 1mm) after stirring 2～4h, just makes sample.
This water-based emulsion is to adopt the dip coating coating.The dip-coating process is, the speed of sample with 300mm/min is dropped in the water-based emulsion, and it is kept 5min at this kind state, then it lifted with the speed of 50mm/min.After coating is finished at 200 ℃ baker inner drying 60min.
(2 μ L) is dropped on the coatingsurface of sample with a pure water.Measure contact angle with contact angle tester (Kyowa interface science, Japan).The result is stated from table 1.
Sample is placed in 375 ℃ the stove.After the time shown in the table 1, measure contact angle and be shown in table 1.
Application example 2
In application example 2, preparation comprise with application example 1 in the water-based emulsion of fluorocarbon silane hydrolysis product of same composition, different is to replace phosphoric acid with boric acid, and the pH value is 4.0.The preparation sample is also implemented the same water test of refusing.Contact angle determination result is stated from table 1.
Comparative Examples 1～5
In Comparative Examples 1～5, prepare the water-based emulsion that contains as application example 1, different is to replace phosphoric acid to regulate pH value to 2.0 with hydrochloric acid, sulfuric acid, nitric acid, acetate and formic acid respectively.The preparation sample is also implemented the same water test of refusing.The result is stated from table 1.
Comparative Examples 6～9
In Comparative Examples 6～9, prepare water-based emulsion as application example 1, different is to use (table 1) ammoniacal liquor, sodium hydroxide, potassium hydroxide and pyridine to replace phosphoric acid to regulate pH value to 8～11 respectively.The preparation sample is also implemented the same water test of refusing.The result is stated from table 1.
Table 1 a
??App1 ??App2 ??Com1 ?Com2 ??Com3 ??Com4 ??Com5 ??Com6 ??Com7 ??Com8 ?Com9
The pH agent ??PA ??BA ???HA ??SA ???NA ??AA ??FA ??AH ??SH ??PH ??Py
Final pH ??2.0 ??4.0 ???2.0 ??2.0 ???2.0 ??2.0 ??2.0 ??10.8 ??11.2 ??11.0 ??8.1
??IWRA ??120 ??120 ???121 ??120 ???119 ??119 ??121 ??118 ??114 ??115 ??120
??WRA-15 ??125 ??112 ???8 ??15 ???8 ??18 ??8 ??120 ??114 ??108 ??118
??WRA-20 ??- ??100 ???- ??- ???- ??- ??- ??- ??- ??- ??-
??WRA-40 ??104 ??- ???- ??- ???- ??- ??- ??97 ??98 ??81 ??95
aThe abbreviation of using is: app, application example; Com, Comparative Examples; PA, phosphoric acid; HA, hydrochloric acid; BA, boric acid; HA, hydrochloric acid; AA, acetate; FA, formic acid; AH, ammonium hydroxide aqueous solution; SH, aqueous sodium hydroxide solution; PH, potassium hydroxide aqueous solution; Py, pyridine; The pH agent, expression is used to regulate acid or the alkali of emulsion pH; Final pH is represented the final pH of emulsion; IWRP representative initially refuse the water angle (°); WRA-15 represent behind 375 ℃ of following 15h refuse the water angle (°); WRA-20 represent behind 375 ℃ of following 20h refuse the water angle (°); WRA-40 represent behind 375 ℃ of following 40h refuse the water angle (°).
Relatively application example 1～2 and Comparative Examples 1～5 have all obtained to have the coating that excellence is refused the water characteristic in all samples.Yet, when emulsion being adjusted to acidic region, identical or higher before the refusing water angle numerical value and wear out of coatingsurface behind 375 ℃ of down aging 15h with phosphoric acid or boric acid.This shows that coating not only has the water of refusing characteristic, and have heat-resisting, refuse the water characteristic.
Compare application example 1～2 and Comparative Examples 6～9, those emulsions that are adjusted to acidic region or basic region have obtained to have the coating that superior heat resistance is refused the water characteristic.Yet, if use phosphoric acid or boric acid, even if coatingsurface refuse water angle numerical value under 375 ℃ through 20 or 40h after still greater than 100 °., adopt alkaline solution then to have and be lower than 100 numerical value as those of catalyzer.In other words, the coating of phosphoric acid or boric acid heat-resisting refused the water characteristic and has and be better than those the weather resistance that contains alkaline pH-conditioning agent.The result shows that also water-based emulsion of the present invention is coated with formed coating long-term excellence that keeps under hot conditions and refuses the water characteristic.
Application example 3～5
Tensio-active agent (the per 100 weight part fluorocarbon silames of 30 weight parts) is dissolved in the water.Slowly add fluorocarbon silame shown in the table 2 (accounting for the 10wt% of whole water miscible liquid weight), utilize traditional stirring means to keep stirring therebetween, with suppress fluorocarbon silame from condensation, and keep fluorocarbon silame to be in hydrolyzed state.When adopting pH meter to measure ph value of emulsion, add acid or pH-conditioning agent shown in the table 2.When reaching the value of final pH shown in the table 2, stop to add.Add (CH 3) Si (OCH 3) 3, until (the CH that obtains 0.45 3) Si (OCH 3) 3With the fluorocarbon silame mol ratio, the result makes emulsion.
After water miscible liquid stirred 2～4h, it is coated on sheet glass, and (2.5cm * 5.0cm, thick: 3mm) surface formed coating, thereby makes sample.
This water-based emulsion is to adopt the dip coating coating.The dip-coating process is, the speed of sample with 300mm/min is dropped in the water-based emulsion, and it is kept 5min at this kind state, then it lifted with the speed of 50mm/min.Place it in 200 ℃ baker inner drying 60min after coating is finished, thereby make sample.
Pure water (2 μ L) is dropped on the coatingsurface of sample.Measure contact angle with contact angle tester (KyowaKaimen Kagaku, Japan).The result is stated from table 2.
To cook oil (10mg) and be sprayed on the coatingsurface of sample, subsequently at 250 ℃ of baking 60min.Erase empyreumatic oil stain as possible 5 times with gauze, detect by an unaided eye then and looked at how much to burn oil stain and be removed.The result is stated from table 2.
Comparative Examples 10～11
In Comparative Examples 1 and 2, preparation form with application example 3 in identical the containing fluorocarbon silame hydrolysate water miscible liquid and prepare sample of water miscible liquid that obtain, different is use four (2-(2-methoxy ethoxy) ethyl) silicon ester (Si (DEGM) 4).Carry out same water test and the anti-spot test for fat refused.The result is stated from table 2.
Comparative Examples 12
In Comparative Examples 12, carry out with application example 3 same refuse water test and same anti-spot test for fat.The result is stated from table 2.
Comparative Examples 13～14
The water miscible liquid that contain fluorocarbon silame hydrolysate identical with application example 3 formed in preparation, and different is, do not use catalyzer in Comparative Examples 13, and employing (Si (DEGM) 4) replace organic methoxy silane.Refuse water and anti-spot test for fat.The result is stated from table 2.
In Comparative Examples 14, the water miscible liquid that contain fluorocarbon silame hydrolysate similar to application example 3 formed in preparation, and different is not use catalyzer.Refuse water and anti-spot test for fat.The result is stated from table 2.
Table 2 a
???App3 ???App4 ??App5 ???Com10 ???Com11 ?Com12 ???Com13 ???Comp ????14
????Si ????OMS ????OMS ??OMS ????SiD ????SiD ??- ????SiD 4 ????OMS
The PH agent ????PA ????HA ??Am ????PA ????HA ??- ????- ????-
Final pH ????2.0 ????2.0 ??10.8 ????2.0 ????2.0 ??- ????5.0 ????5.0
Base material Glass Glass Glass Glass Glass Glass Glass Glass
????PCA ????120 ????120 ??119 ????120 ????119 ??121 ????119 ????118
????DRBS ????Comp ????CompE ??Comp ????SR ????SR ??None ????SR ????SR
aAbbreviation is referring to the note of table 1.Unlistedly in table 1 be: Si, the type of silicon compound; OMS, organic methoxy silane; SiD, Si (DEGM) 4Am, ammonia;-, do not exist or undetermined; PCA, contact angle (°); And IDRBS, and oil stain removal degree (Comp, oil stain is almost completely removed; CompE, oil stain is removed substantially fully; SR, oil stain still has; None, oil stain is not removed).
In application example 3, only have very small amount of oil to remain in glass surface, but by wiping, all oil all can be removed easily and almost entirely.In application example 4, the wiping of oil is removed than application example 3 difficulties, but nearly all burn oil stain and all can remove.In application example 5, oil stain can be removed easily and almost entirely.
In Comparative Examples 12, not burning oil stain can remove by the glass surface of wiping coating.The Comparative Examples 10,11 that oil spread and being retained in obtains with the product that contains silicon ester and 13 in glass surface on.With not containing the pH-conditioning agent, and contain in the Comparative Examples 14 that the product of organic methoxy silane obtains, oily spread also keeps.
The above results shows that the laminar surface that is coated with the composition that comprises organic methoxy silane or silicon ester shows good water repellency.Anti-oil stain has obtained sizable improvement by adopting organic methoxy silane complex acid or pH-conditioning agent.Adopt phosphoric acid, further improved anti-oil stain.
Application example 6～7
The water miscible liquid that preparation is identical with application example 3 and with its be applied in sheet glass (2.5cm * 5.0cm, thick: 3mm) formation coating, thus make sample.
Pure water (2 μ L) is dropped on the coatingsurface of sample.Measure contact angle with contact angle tester (KyowaKaimen Kagaku, Japan).The result is stated from table 3.
Each sample is placed in 330 ℃ the baker, measures contact angle through 6h and the aging back of 10h by similar approach.The result is stated from table 3.
Comparative Examples 15～17
Prepare water miscible liquid with the method identical with application example 3, different is to substitute organic methoxy silane with silicon dioxide compound shown in the table 3.With its be applied in sheet glass (2.5cm * 5.0cm, thick: as 3mm) to form coating, thereby make per sample (p.s.).On each sample, measure contact angle like that by being similar to application example 6.The result is stated from table 3.
Table 3 a
????App6 ???App7 ???Com15 ???Com16 ????Com17
????Si ????OMS ????OMS ????EpS ????AS ????ECS
????pH ????PA ????HA ????PA ????PA ????PA
Final pH ????2.2 ????2.2 ????2.2 ????2.2 ????2.2
Base material Glass Glass Glass Glass Glass
????PWRA ????116 ????114 ????116 ????117 ????116
????WRA-6 ????138 ????112 ????101 ????46 ????109
????WRA-10 ????137 ????113 ????73 ????33 ????97
aNote referring to table 1 and 2.What do not provide in table 2 is: EpS, epoxy silane; AS, aminosilane; ECS, epoxycyclohexyl silane; PWRA, once refuse the water angle (°); WRA-6,330 ℃ through behind the 6h refuse the water angle (°); WRA-10,330 ℃ through behind the 10h refuse the water angle (°).
In application example 6, to refuse the water angle through the coatingsurface behind 6h and the 10h at 300 ℃ and be better than before aging, this shows the coating that has obtained at high temperature to have good water repellency.
In Comparative Examples 15～17, once refuse the water angle by what adopt silicon compound beyond organic methoxy silane to obtain to be similar in application example 6, to obtain, and obtain to have the coating of water repellency.Yet behind 330 ℃ of process 10h, every kind the water angle of refusing has all reduced, even if adopt phosphoric acid, and the none coating has any water repellency at high temperature.
Application example 7 wherein adopts the water miscible liquid that contains organic methoxy silane as application example 6, shows, coating has good water repellency at high temperature, although with hydrochloric acid as the pH-conditioning agent.
Application example 8
Preparation be similar to application example 3 water miscible liquid and with its be coated on aluminium sheet (JIS1100 2.5cm * 5.0cm, thick: as 1mm), thereby to obtain sample.
Pure water (2 μ L) is dropped on the coatingsurface of sample.Measure contact angle with contact angle tester (KyowaKaimen Kagaku, Japan).The result is stated from table 4.
Per sample (p.s.) is placed in 370 ℃ the baker, behind the 40h, measures contact angle similarly.The result is stated from table 4.
Comparative Examples 18～21
Produce every kind of water miscible liquid identical with application example 3, different is silicon compound shown in the employing table 4.With its be coated on aluminium sheet (JIS1100 2.5cm * 5.0cm, thick: as 1mm), thereby to obtain sample.Measure contact angle as application example 6.The result is stated from table 4.
Table 4 a
???App8 ???Com18 ???Com19 ???Com20 ???Com21
?Si ????OMS ????SiD ????SiD ????SiD ????OMS
The pH agent ????PA ????HA ????PA ????AH ????-
Final pH ????2.2 ????2.2 ????2.2 ????10.8 ????5.0
Base material Aluminium Aluminium Aluminium Aluminium Aluminium
?PWRA ????120 ????117 ????120 ????112 ????118
?WRA-40 b ????105 ????10 ????15 ????45 ????31
aNote referring to the front.
bTemperature is 370 ℃.
Application example 8 and Comparative Examples 18～21 have roughly the same once refusing and show that every kind of coating all has good water repellency in the water angle.Yet, adopt in the Comparative Examples 18～20 be silicon ester 370 ℃ down through it is refused the water angle and significantly diminishes behind the 40h, and application example 8 370 ℃ through have behind the 40h 105 ° refuse the water angle.This result shows and adopts organic methoxy silane can obtain to have the coating of good water repellency and good durability under the high temperature.
Comparative Examples 21 370 ℃ through having the much lower water angle of refusing behind the 40h, even if show and adopt organic methoxy silane,, still can not produce water repellency good under the high temperature if lack catalyzer.
Above presentation of results, the coating of being produced by the water miscible liquid that contains fluorocarbon silame or its hydrolysate shows good water repellency and good resistance oil stain ability under the high temperature.Oil stain can be removed effectively easily by applying the prepared coated product of water miscible liquid of the present invention, and good water repellency can be at high temperature kept.

Claims (13)

1. composition that comprises fluorocarbon silame or its hydrolysate, tensio-active agent, polymerizable silicon-containing compound and catalyzer, wherein said fluorocarbon silame has general formula R f-(CH 2) p-Si{-(O-CH 2CH 2) n-OR ' } 3, R fBe C 3-18Perfluoro alkyl group or its combination, each R ' is C independently 1-3Alkyl group or its combination, p is 2～4, comprises 2 and 4, and n is 2～10, comprises 2 and 10; Described silicon-containing compound is selected from silicon ester, organosilane and combination thereof; And described catalyzer is phosphoric acid, boric acid or its combination, if described silicon-containing compound is the words of described silicon ester.
2. the composition of claim 1, wherein said silicon-containing compound is to have general formula Si-R 4Silicon ester, R is selected from OCH 3, OCH 2CH 3, (OCH 2CH 2) mOCH 3And combination, and m is 1～10, comprises 1 and 10.
3. the composition of claim 1, wherein said silicon-containing compound is an organoalkoxysilane, has general formula R 2 qSi (OR 3) 4-q, each R 2Be the alkyl group of 1～10 carbon atom independently, each R 3Be the alkyl group of 1～about 3 carbon atoms independently, and q is 1～3, comprises 1 and 3.
4. claim 1,2 or 3 composition, wherein said fluorocarbon silame is selected from perfluor alkyl ethide three (2-(2-methoxy ethoxy) oxyethyl group) silane, (2-(2-(2-methoxy ethoxy) oxyethyl group) oxyethyl group) silane, and their combination.
5. claim 1,2,3 or 4 composition, wherein tensio-active agent has the HLB value greater than 12.
6. the composition of claim 5, wherein tensio-active agent has the HLB value greater than 16.
7. claim 5 or 6 composition, wherein tensio-active agent is selected from R ' f-CH 2CH 2-O-(CH 2CH 2O) 11-H, C 9H 19-C 6H 4-O-(CH 2CH 2O) 50-H, R ' f-CH 2CH 2SCH 2CH (OH) CH 2N (CH 3) 3 +Cl -, C 12H 25(OCH 2CH 2) 4OSO 3 -NH 4 +, C 12H 27-C 6H 4-SO 3 -Na +And combination, R ' fIt is perfluoro alkyl group with about 3～18 carbon atoms.
8. claim 1,2,4,5,6 or 7 composition, wherein said silicon-containing compound is Si-((OCH 2CH 2) 2OCH 3) 4
9. claim 1,2,3,5,6 or 7 composition, wherein said silicon-containing compound is organic methoxy silane.
10. claim 1,2,4,5,6,7 or 8 composition, wherein said catalyzer is the acid that is selected from phosphoric acid, boric acid and combination thereof.
11. claim 1,2,3,5,6,7 or 9 composition, wherein said catalyzer is selected from phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, nitric acid, acetate, oxalic acid, ammonia, pyridine, sodium hydroxide or potassium hydroxide and combination thereof.
12. a method comprises: surfactant dissolves is generated tensio-active agent-water mixture in water; Described tensio-active agent-water mixture and fluorocarbon silame are lumped together generation silane-surfactant mixture; Described silane-surfactant mixture and catalyzer are lumped together the mixture that pH was regulated in generation; And with described mixture and a kind of emulsion of polymerizable silicon-containing compound merging generation of regulating pH, described in wherein said tensio-active agent, described fluorocarbon silame, described catalyzer and described silicon-containing compound such as above any one claim.
13. one kind comprises the method that makes substrate surface contact with a kind of composition, wherein said composition is as in the claim 1～11 as described in any one, and described base material is metal, glass, ceramic tile, brick, concrete, timber, masonry, fiber, leather, plastics or stone.
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